Ion exchangeable glass with high damage resistance

ABSTRACT

An ion exchangeable glass having a high degree of resistance to damage caused by abrasion, scratching, indentation, and the like. The glass comprises alumina, B 2 O 3 , and alkali metal oxides, and contains boron cations having three-fold coordination. The glass, when ion exchanged, has a Vickers crack initiation threshold of at least about 30 kilogram force.

This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application Ser. No. 61/653,485 filed on May 31, 2012 the content of which is relied upon and incorporated herein by reference in its entirety.

BACKGROUND

The disclosure relates to glasses that are capable of chemical strengthening by ion exchange and have intrinsic damage resistance. More particularly, the disclosure relates to such glasses that are strengthened by ion exchange and possess resistance to damage by abrasion, scratching, indentation, and other forms of sharp contact.

The ion exchange process provides a substantial improvement of glasses that are capable of being strengthened by this process to resist damage by sharp impact or indentation. To date, glasses containing network modifiers such as alkali and alkaline earth cations have been used. These cations form non-bridging oxygens (oxygens bonded to only one silicon atom), which reduce the resistance of the ion exchanged glass to damage introduced by abrasion, scratching, or the like.

SUMMARY

The present disclosure provides an ion exchangeable glass having a high degree of resistance to damage caused by abrasion, scratching, indentation, and the like. The glass comprises alumina, B₂O₃, and alkali metal oxides, and contains boron cations having three-fold coordination. The glass, when ion exchanged, has a Vickers crack initiation threshold of at least about 30 kilogram force (kgf).

Accordingly, one aspect of the disclosure is to provide an ion exchangeable glass comprising at least about 50 mol % SiO₂; at least about 10 mol % R₂O, wherein R₂O comprises Na₂O; Al₂O₃, wherein −0.5 mol %≦Al₂O₃ (mol %)−R₂O(mol %)≦2 mol %; and B₂O₃, and wherein B₂O₃ (mol %)−(R₂O(mol %)−Al₂O₃ (mol %))≧4.5 mol %.

A second aspect of the disclosure is to provide a glass comprising at least about 50 mol % SiO₂; at least about 10 mol % R₂O, wherein R₂O comprises Na₂O; Al₂O₃; and B₂O₃, wherein B₂O₃ (mol %)−(R₂O(mol %)−Al₂O₃ (mol %))≧4.5 mol %, and wherein the glass has a zircon breakdown temperature that is equal to the temperature at which the glass has a viscosity of greater than about 40 kPoise.

A third aspect of the disclosure is to provide an ion exchanged glass having a Vickers crack initiation threshold of at least about 30 kgf. The glass comprises at least about 50 mol % SiO₂; at least about 10 mol % R₂O, wherein R₂O comprises Na₂O; Al₂O₃, wherein −0.5 mol %≦Al₂O₃ (mol %)−R₂O(mol %)≦2 mol %; and B₂O₃, wherein B₂O₃ (mol %)−(R₂O(mol %)−Al₂O₃ (mol %))≧4.5 mol %.

These and other aspects, advantages, and salient features will become apparent from the following detailed description and the appended claims.

DETAILED DESCRIPTION

In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range as well as any ranges therebetween. As used herein, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more,” unless otherwise specified. It also is understood that the various features disclosed in the specification can be used in any and all combinations.

As used herein, the terms “glass” and “glasses” includes both glasses and glass ceramics. The terms “glass article” and “glass articles” are used in their broadest sense to include any object made wholly or partly of glass and/or glass ceramic.

It is noted that the terms “substantially” and “about” may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

Unless otherwise specified, all compositions and concentrations described herein are expressed in mole percent (mol %). It is understood that the compositional ranges described and claimed herein represent the bulk composition of the glass as determined by those means skilled in the art, and are applicable to both the unstrengthened and strengthened glasses described herein.

Accordingly, a glass having intrinsic damage resistance is provided. In one aspect, the glass, which may be strengthened so as to be resistant to damage via sharp impact, comprises at least about 50 mol % SiO₂; at least about 10 mol % of at least one alkali metal oxide R₂O, wherein R₂O includes Na₂O and, optionally, other alkali metal oxides (e.g., Li₂O, K₂O, Ce₂O, Rb₂O); alumina (Al₂O₃), wherein −0.5 mol %≦Al₂O₃ (mol %)−R₂O(mol %)≦2 mol %; and boron oxide (B₂O₃), wherein B₂O₃ (mol %)−(R₂O(mol %)−Al₂O₃ (mol %))≧4.5 mol %.

In another aspect, the glass comprises at least about 50 mol % SiO₂; Al₂O₃; B₂O₃; and at least about 10 mol % R₂O, wherein R₂O comprises Na₂O; wherein B₂O₃−(R₂O—Al₂O₃)≧4.5 mol %, and wherein the glass has a zircon breakdown temperature (i.e., the temperature at which zircon breaks down to form zirconia and silica) equal to the temperature at which the viscosity of the glass is greater than about 40 kPoise.

In some aspects, the glasses described herein are ion exchangeable; i.e., cations—typically monovalent alkali metal cations—which are present in these glasses are replaced with larger cations—typically monovalent alkali metal cations, although other cations such as Ag⁺ or Tl⁺—having the same valence or oxidation state. The replacement of smaller cations with larger cations creates a surface layer that is under compression, or compressive stress CS. This layer extends from the surface into the interior or bulk of the glass to a depth of layer DOL. The compressive stress in the surface layers of the glass are balanced by a tensile stress, or central tension CT, in the interior or inner region of the glass. Compressive stress and depth of layer are measured using those means known in the art. Such means include, but are not limited to measurement of surface stress (FSM) using commercially available instruments such as the FSM-6000, manufactured by Luceo Co., Ltd. (Tokyo, Japan), or the like, and methods of measuring compressive stress and depth of layer are described in ASTM 1422C-99, entitled “Standard Specification for Chemically Strengthened Flat Glass,” and ASTM 1279.19779 “Standard Test Method for Non-Destructive Photoelastic Measurement of Edge and Surface Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat Glass,” the contents of which are incorporated herein by reference in their entirety. Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the stress-induced birefringence of the glass. SOC in turn is measured by those methods that are known in the art, such as fiber and four point bend method, both of which are described in ASTM standard C770-98 (2008), entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety, and a bulk cylinder method.

In other aspects, the glasses described herein are ion exchanged and have surfaces layers under compression to a depth of layer and an inner region that is under a tensile stress, as described hereinabove. In one aspect, the ion exchanged glass comprises at least about 50 mol % SiO₂; Al₂O₃; B₂O₃; and at least about 10 mol % R₂O, wherein R₂O comprises Na₂O; and wherein −0.5 mol %≦Al₂O₃ (mol %)−R₂O(mol %)≦2 mol % and B₂O₃ (mol %)−(R₂O(mol %)−Al₂O₃ (mol %))≧4.5 mol %. The ion exchanged glass has a Vickers crack initiation threshold of at least about 30 kilogram force (kgf).

When present in boroaluminosilicate glasses, alkali metals act as charge-balancing cations for tetrahedrally coordinated aluminum and boron. Species similar to RAlO₂ or RBO₂, where R is an alkali metal and aluminum are Al^(3′) and B³⁺, for example, are four-fold coordinated by oxygen. The four oxygen atoms surrounding aluminum or boron are presumed to bond to silicon atoms. Each oxygen therefore obtains one electron from the silicon atoms and, in effect, ¾ of an electron, from the tetrahedrally coordinated Al³⁺ or B³⁺. An alkali metal donates an electron to this configuration, thus allowing all four oxygens in the tetrahedron to obtain a full electron shell. The large alkaline earth elements Ca, Sr, and Ba are known to fill this role for aluminum. Thus, in a boroaluminosilicate glass in which R₂O(mol %)+CaO(mol %)+SrO(mol %)+BaO(mol %)−Al₂O₃ (mol %)−B₂O₃ (mol %)=0 mol % or, alternatively, (Al₂O₃ (mol %)+B₂O₃ (mol %))/(R₂O(mol %)+CaO(mol %)+SrO(mol %)+BaO(mol %))=1, there are exactly as many electrons to be donated from alkalis and alkaline earths as there are tetrahedrally coordinated aluminum and boron atoms in need of charge balance. When R₂O(mol %)+CaO(mol %)+SrO(mol %)+BaO(mol %)−Al₂O₃ (mol %)−B₂O₃ (mol %)<0 (mol %), there are more aluminum and boron atoms in need of charge balance than electrons available from charge-balancing alkali or alkaline earth cations. Such glasses generally have high intrinsic damage resistance, which is considerably enhanced after ion exchange.

Aluminum is nearly always four-fold coordinated by oxygen if there are enough charge-balancing cations available, large. Low-valence cations perform better in a charge-balancing role than small, higher valence cations. This has been attributed to the extent to which the charge-balancing cation competes with aluminum for electron density. Large, low-valence cations are ineffective in this competition and thus leave electron density largely within the AlO₄ tetrahedron. Boron is mostly four-fold coordinated in annealed alkali borosilicate glasses in which the amount of alkali metals present in the glass is greater than that of boron. In annealed boroaluminosilicate glasses, however, boron assumes a mix of three and four-fold coordination, even in charge-balanced compositions. In glasses along the mixing line between 12.5Na₂O-12.5Al₂O₃-75SiO₂ and 12.5Na₂O-12.5B₂O₃-75SiO₂, for example, boron adopts a mix of three- and four-fold coordination. To a reasonable approximation, then, charge-balancing cations first stabilize aluminum in four-fold coordination, and the remaining cations will stabilize some fraction of boron in four-fold coordination, where the fraction may be as high as 1. The glasses described herein comprise greater than about 4.5 mol % B₂O₃ in which the boron cations are three-fold coordinated.

When R₂O(mol %)+MO(mol %)<Al₂O₃ (mol %), where MO represent divalent metal oxides (e.g., MgO, ZnO, CaO, BaO, SrO, etc.), there are not enough monovalent or divalent cations to stabilize aluminum in four-fold coordination, and boron is therefore almost entirely in three-fold coordination in these glasses. Three-fold coordinated boron is desirable because it can potentially increase to four-fold coordination when compressed, thus providing damage resistance to the glass. Glasses with compositions in which M₂O(mol %)+RO(mol %)−Al₂O₃ (mol %)<0 mol %, however, generally have very high melting temperatures unless they also have very high B₂O₃ contents, e.g., greater than about 10 mol %. Such high amounts of B₂O₃ have a deleterious effect on both the surface compressive stress and rate of ion exchange, as evidenced by low depths of layer obtained in an ion exchange of fixed duration/time period. Since high CS (e.g., greater than about 650 MPa) and significant depth of layer (DOL) (e.g., greater than 30 μm) are also required to obtain good damage resistance, the additional benefits of high intrinsic damage resistance may be offset by poor ion exchange characteristics. In order to achieve the optimal balance of attributes after ion exchange, it is therefore desirable to keep boron concentrations low. Accordingly, in some embodiments, the glasses described herein comprise less than 10 mol % B₂O₃. Such glasses are very difficult to melt to a level of quality (e.g., defect concentration) acceptable for mass manufacturing. Depending on the application for the glass article, a marginally acceptable defect level in a continuous process is about one inclusion greater than 100 μm in diameter per kilogram (kg) of glass.

In some embodiments, the glasses described herein comprise at least about 50 mol % SiO₂, from about 9 mol % to about 22 mol % Al₂O₃; from about 4.5 mol % to about 10 mol % B₂O₃; from about 10 mol % to about 20 mol % Na₂O; from 0 mol % to about 5 mol % K₂O; at least about 0.1 mol % MgO and/or ZnO, wherein 0≦MgO+ZnO≦6; and, optionally, at least one of CaO, BaO, and SrO, wherein 0 mol %≦CaO+SrO+BaO≦2 mol %. In some embodiments, the glasses described herein comprise from about 66 to 74 mol % SiO₂.

In some embodiments, the glasses described herein comprise at least about 0.1 mol % of at least one of MgO and ZnO. In certain embodiments, the glass may comprise up to about 6 mol % MgO and/or ZnO. Magnesium and zinc behave differently from the other divalent cations. While magnesium and zinc may charge-balance aluminum to some extent, they appear to have little or no role in stabilizing boron in four-fold coordination. Thus, replacing an alkali oxide with magnesium oxide in a boroaluminosilicate glass forces boron atoms out of four-fold coordination and into three-fold coordination, resulting in higher Vickers crack initiation threshold loads in ion-exchanged glass.

In addition to the oxides listed above, the glasses described herein may further comprise chemical fining agents including, but not limited to, halogens or halides (compounds containing F, Cl, Br and I) and at least one of the oxides As₂O₃, Sb₂O₃, CeO₂ and SnO₂. These fining agents, when present, are generally batched in to the raw material at a level of about 0.5 mol % or less, and have minor impact on both the rate of ion exchange and the compressive stress that are ultimately obtained.

In addition, other oxides may be added at low concentrations with little or no impact on the ion exchange characteristics of these glasses. Examples of such oxides include ZrO₂, which is a common contaminant introduced by zirconia refractories in melters; TiO₂, which is a common tramp component of natural silica sources; Fe₂O₃, which is an ubiquitous tramp oxide in all but the purest chemical reagents; and other transition metal oxides that may be used to introduce color. These transition metal oxides include V₂O₅, Cr₂O₃, Co₃O₄, Fe₂O₃, MnO₂, NiO, CuO, Cu₂O, and the like. Concentrations of these oxides, when present in the glass, are kept at levels of less than or equal to about 2 mol %. Compared to calcium, larger alkaline earths such as Sr and Ba lead to lower diffusivity and thus significantly lower depth of the compressive layer. Because Sr and Ba are costly reagents compared to most of the other oxides in the glasses described herein the concentrations of these materials, when present in the glass, are kept at levels of no more than about 0.5 mol %. Rubidium and cesium oxides are too large to ion exchange at an appreciable rate, are costly, and contribute to high liquidus temperatures at elevated concentrations. The concentrations of these oxides are therefore kept below 0.5 mol %. Lithium oxide is to be generally avoided, as it contributes to “poisoning” of potassium nitrate salt ion exchange baths, resulting in lower compressive stress than if the same glass were ion exchanged in a lithium-free salt bath. In addition, compared to a sodium-for-potassium exchange, the presence of lithium leads to significantly reduced diffusivity when exchanging for potassium. When present in the glass, the lithium oxide concentration should therefore be kept below about 0.5 mol %, and, in some embodiments, below about 0.1 mol %. In some embodiments, the glasses described herein are substantially free of lithium.

Non-limiting examples of the glasses described herein are listed in Table 1. Table 2 lists selected properties, including strain, anneal, and softening temperatures, coefficients of thermal expansion (CTE), density, Poisson ratio, shear moduli, Young's moduli, stress optical coefficients (SOC), and refractive indices, of the samples listed in Table 1

As used herein, the term “zircon breakdown temperature” or “T^(breakdown)” refers to the temperature at which zircon—which is commonly used as a refractory material in glass processing and manufacture—breaks down to form zirconia and silica. In isoviscous processes such as fusion, the highest temperature experienced by the glass corresponds to a particular viscosity of the glass. For example, “T^(35kP)” refers to the temperature at which the glass has a viscosity of 35 kilopoise (kPoise). The difference between the breakdown temperature and the temperature corresponding to 35,000 poise viscosity is defined as the breakdown margin T^(margin), where: T^(margin)=T^(breakdown)−T^(35kp). When the breakdown margin T^(margin) is negative, zircon will breakdown to form zirconia defects at some location on the isopipe. When T^(margin) is zero, it is still possible that temperature excursions could cause zircon breakdown to occur. It is therefore desirable not only to make the breakdown margin positive, but to maximize T^(margin) as much as possible while being consistent with all the other attributes that must be maintained in the final glass product. In some embodiments, the glasses described herein have a zircon breakdown temperature that is greater than 40 kPoise and, in some embodiments, about 70 kPoise.

In those embodiments in which the glass is strengthened by ion exchange, the glass may, in some embodiments, be ion exchanged to create a surface layer that is under a compressive stress of at least about 600 megapascals (MPa) and, in other embodiments, at least about 800 MPa. The compressive surface layer has a depth of layer of at least about 30 microns (μm). The ion exchanged glasses described herein also possess a degree of intrinsic damage resistance (IDR), which may be characterized by the Vickers crack initiation threshold of the ion exchanged glass. In some embodiments, the ion exchanged glass has a Vickers crack initiation threshold in a range from about 30 kgf to about 35 kgf. The Vickers crack initiation threshold measurements described herein are performed by applying and then removing an indentation load to the glass surface at a rate of 0.2 mm/min. The maximum indentation load is held for 10 seconds. The crack initiation threshold is defined at the indentation load at which 50% of 10 indents exhibit any number of radial/median cracks emanating from the corners of the indent impression. The maximum load is increased until the threshold is met for a given glass composition. All indentation measurements are performed at room temperature in 50% relative humidity.

When ion exchanged, the glasses described herein have a compressive stress that is sufficiently high to provide outstanding damage resistance against impact of various kinds. The glasses described herein may be ion exchanged at a rate that facilitates large scale manufacturing. While it is advantageous to provide high compressive stress by annealing the glass prior to ion exchange, a high compressive stress may also be obtained by instead cooling the glass rapidly from a high temperature (e.g., above the strain point of the glass). Such rapid cooling may occur, for example, in down drawn processes such as fusion or slot draw processes. The combination of compressive stress, depth of layer, and intrinsic damage resistance of the ion exchanged glasses described herein provides excellent resistance to visible or strength-limiting damage introduced via sharp contact and scratching.

Table 3 lists compressive stresses, depths of layer (DOL), and indentation thresholds for samples listed in Table 1 that were ion exchanged.

TABLE 1 Composition (mol %) Example SiO₂ Al₂O₃ B₂O₃ Na₂O K₂O MgO CaO ZnO SnO₂ 1 64.85 13.01 6.81 13.09 0.51 1.53 0.08 0.00 0.10 2 64.92 12.88 6.57 12.90 0.51 2.04 0.08 0.00 0.10 3 64.93 12.70 6.47 12.69 0.51 2.52 0.08 0.00 0.10 4 64.94 12.50 6.30 12.51 0.51 3.04 0.09 0.00 0.10 5 65.10 13.01 6.39 12.28 0.51 2.52 0.08 0.00 0.10 6 65.16 13.47 6.39 11.73 0.51 2.55 0.08 0.00 0.10 7 65.08 13.22 6.31 13.19 0.51 1.50 0.08 0.00 0.10 8 65.13 13.10 6.07 12.97 0.51 2.03 0.08 0.00 0.10 9 65.08 12.96 5.78 13.00 0.51 2.49 0.09 0.00 0.10 10 65.24 12.91 5.47 12.67 0.51 3.01 0.09 0.00 0.10 11 64.78 12.87 5.55 13.11 0.51 2.08 1.00 0.00 0.10 12 51.33 20.21 7.03 19.17 0.97 1.03 0.13 0.00 0.10 13 65.10 13.15 5.95 14.60 0.50 0.50 0.07 0.00 0.10 14 64.71 13.14 5.98 14.47 0.50 0.99 0.07 0.00 0.10 15 64.05 13.18 5.97 14.60 0.50 1.51 0.08 0.00 0.10 16 63.65 13.16 5.97 14.51 0.49 2.00 0.08 0.00 0.10 17 63.17 13.16 5.96 14.50 0.49 2.50 0.08 0.00 0.10 18 57.52 17.04 5.58 18.17 0.49 0.99 0.08 0.00 0.10 19 57.53 17.00 5.58 18.16 0.49 1.02 0.08 0.00 0.10 20 63.39 14.04 7.02 13.84 0.50 1.03 0.07 0.00 0.10 21 64.38 13.01 7.06 13.83 0.50 1.03 0.07 0.00 0.10 22 64.48 14.03 5.97 13.81 0.50 1.03 0.07 0.00 0.10 23 64.57 14.03 7.00 12.71 0.49 1.01 0.07 0.00 0.10 24 64.47 14.01 7.01 13.78 0.00 0.53 0.07 0.00 0.10 25 64.37 12.00 7.12 13.80 0.49 2.04 0.07 0.00 0.10 26 63.39 14.00 6.91 14.08 0.51 0.01 0.06 0.92 0.10 27 64.22 12.98 7.03 14.16 0.52 0.01 0.06 0.90 0.10 28 64.34 14.00 5.99 14.06 0.51 0.01 0.06 0.91 0.10 29 64.27 13.94 7.04 13.12 0.52 0.01 0.06 0.92 0.10 30 64.37 13.96 7.02 13.97 0.01 0.01 0.06 0.48 0.10 31 64.28 11.99 7.04 14.21 0.50 0.01 0.06 1.79 0.10 32 67.18 12.78 5.65 13.70 0.00 0.54 0.02 0.00 0.10 33 65.52 13.59 5.62 14.25 0.10 0.77 0.04 0.00 0.10 34 65.61 13.58 5.59 14.21 0.10 0.76 0.04 0.00 0.10 35 65.74 13.57 5.63 14.05 0.10 0.77 0.04 0.00 0.10 36 65.71 13.57 5.74 13.97 0.10 0.76 0.04 0.00 0.10 37 65.86 13.56 5.25 14.32 0.10 0.76 0.04 0.00 0.10 38 65.83 13.59 5.12 14.45 0.10 0.77 0.05 0.00 0.10 39 64.53 13.99 6.60 13.71 0.50 0.49 0.06 0.00 0.10 40 64.32 14.00 6.15 13.82 0.51 1.01 0.06 0.00 0.10 41 64.76 13.97 5.57 13.56 0.50 1.45 0.06 0.00 0.10 42 64.53 13.98 5.06 13.74 0.51 2.00 0.06 0.00 0.10 43 64.33 14.01 4.58 13.82 0.51 2.57 0.06 0.00 0.10 44 64.34 14.72 6.18 13.43 0.20 1.01 0.02 0.00 0.07 45 64.21 14.68 5.73 13.51 0.20 1.54 0.03 0.00 0.07 46 64.11 14.71 5.22 13.55 0.20 2.10 0.03 0.00 0.07 47 63.98 14.65 4.65 13.71 0.21 2.68 0.03 0.00 0.07 48 64.09 14.61 4.15 13.61 0.21 3.20 0.03 0.00 0.07 49 66.46 14.20 5.13 11.89 0.20 2.01 0.03 0.00 0.07 50 66.40 13.96 5.13 12.16 0.20 2.03 0.03 0.00 0.07 51 66.44 13.69 5.15 12.37 0.20 2.03 0.02 0.00 0.07 52 66.44 13.46 5.15 12.63 0.20 2.01 0.03 0.00 0.07 53 66.42 13.04 5.11 13.10 0.20 2.01 0.03 0.00 0.07 54 66.45 13.10 5.11 13.00 0.20 2.01 0.03 0.00 0.07 55 64.53 13.91 6.61 13.72 0.10 1.02 0.02 0.00 0.07 56 64.48 13.96 6.04 13.21 0.10 2.10 0.03 0.00 0.07 57 64.29 13.91 5.64 12.79 0.10 3.15 0.03 0.00 0.07 58 64.11 13.87 5.10 12.42 0.10 4.27 0.04 0.00 0.07 59 64.41 13.86 4.57 11.77 0.10 5.14 0.05 0.00 0.07 60 65.76 13.87 5.15 13.91 0.11 1.08 0.03 0.00 0.07 61 65.71 13.90 5.15 13.42 0.11 1.60 0.04 0.00 0.07 62 65.74 13.87 5.08 12.94 0.11 2.13 0.04 0.00 0.07 63 65.87 13.89 5.09 12.32 0.11 2.60 0.04 0.00 0.07 64 65.93 13.93 5.05 11.77 0.11 3.08 0.05 0.00 0.07 65 64.31 14.72 4.06 13.45 0.20 3.13 0.04 0.00 0.07 66 64.44 14.73 3.51 13.39 0.20 3.61 0.04 0.00 0.07 67 64.36 14.76 3.05 13.39 0.20 4.12 0.04 0.00 0.07 68 67.78 13.46 3.46 12.28 0.10 2.79 0.04 0.00 0.07 69 67.63 13.22 3.45 12.61 0.10 2.87 0.04 0.00 0.07 70 67.77 13.01 3.49 12.74 0.10 2.76 0.04 0.00 0.07 71 57.32 19.10 4.37 17.73 0.25 1.06 0.05 0.00 0.10 72 57.42 18.59 5.35 17.17 0.26 1.06 0.05 0.00 0.10 73 67.20 12.08 2.54 14.18 0.00 3.80 0.05 0.00 0.10 74 66.34 12.71 3.57 13.94 0.00 3.28 0.05 0.00 0.09 75 65.10 13.70 4.91 13.72 0.00 2.48 0.04 0.00 0.08 76 65.13 13.77 4.93 13.68 0.00 2.41 0.04 0.00 0.08 77 64.88 13.87 5.20 13.65 0.00 2.32 0.04 0.00 0.08 78 64.91 13.88 5.15 13.61 0.00 2.32 0.05 0.00 0.08 79 64.88 13.90 5.25 13.59 0.00 2.30 0.04 0.00 0.08 80 64.81 13.91 5.22 13.68 0.00 2.31 0.04 0.00 0.08 81 64.65 13.93 5.11 13.75 0.00 2.38 0.14 0.00 0.08 82 64.74 13.98 4.48 14.21 0.00 2.45 0.08 0.00 0.08 83 64.74 14.04 3.90 14.61 0.00 2.54 0.08 0.00 0.08 84 64.66 14.02 3.78 14.80 0.00 2.56 0.09 0.00 0.08 85 64.63 14.02 3.75 14.87 0.00 2.58 0.05 0.00 0.08 86 64.47 14.02 3.84 14.56 0.00 2.98 0.05 0.00 0.08 87 64.73 14.03 3.67 13.89 0.00 3.55 0.05 0.00 0.07 88 64.68 14.02 3.75 13.68 0.00 3.74 0.05 0.00 0.08 89 64.67 14.01 3.80 13.55 0.00 3.83 0.05 0.00 0.08 90 64.82 14.02 3.65 13.54 0.00 3.83 0.05 0.00 0.09 91 64.72 14.01 3.70 13.49 0.00 3.93 0.05 0.00 0.08 92 64.71 13.99 3.78 13.73 0.00 3.67 0.05 0.00 0.07 93 64.87 13.97 3.78 13.84 0.00 3.41 0.04 0.00 0.08 94 64.83 13.95 3.92 14.09 0.00 3.09 0.04 0.00 0.08 95 64.75 13.99 3.97 14.15 0.00 3.01 0.04 0.00 0.08 96 64.66 13.98 4.09 14.15 0.00 2.99 0.04 0.00 0.08 97 64.81 13.99 3.96 14.14 0.00 2.97 0.04 0.00 0.08 98 65.02 13.81 4.10 13.99 0.00 2.97 0.04 0.00 0.08 99 65.97 13.49 3.82 13.69 0.00 2.90 0.04 0.00 0.07 100 66.55 13.18 3.86 13.48 0.00 2.81 0.04 0.00 0.07 101 66.87 13.08 3.83 13.31 0.00 2.79 0.04 0.00 0.07 102 67.04 13.07 3.72 13.26 0.00 2.79 0.04 0.00 0.07 103 66.93 13.06 3.73 13.26 0.00 2.90 0.04 0.00 0.07 104 66.63 12.96 3.58 13.09 0.00 3.62 0.04 0.00 0.07 105 66.10 12.86 3.46 12.89 0.00 4.54 0.05 0.00 0.08 106 65.83 12.81 3.46 12.92 0.00 4.84 0.05 0.00 0.07 107 65.95 12.80 3.36 12.81 0.00 4.94 0.05 0.00 0.07 108 65.98 12.80 3.28 12.82 0.00 4.97 0.05 0.00 0.07 109 65.82 12.84 3.54 12.94 0.00 4.73 0.05 0.00 0.08 110 64.57 13.21 4.72 13.43 0.00 3.97 0.05 0.00 0.08 111 64.27 13.61 5.54 13.40 0.00 3.12 0.04 0.00 0.09 112 63.64 13.87 6.15 13.71 0.00 2.60 0.04 0.00 0.08 113 63.16 13.75 6.57 13.82 0.00 2.56 0.04 0.00 0.09 114 63.37 13.84 6.43 13.79 0.00 2.54 0.04 0.00 0.09 115 63.80 13.76 6.19 13.67 0.01 2.54 0.04 0.00 0.09 116 65.44 13.63 5.22 13.11 0.01 2.52 0.04 0.00 0.07 117 67.21 13.41 4.31 12.46 0.01 2.49 0.04 0.00 0.07 118 68.71 13.27 3.42 12.02 0.00 2.46 0.04 0.00 0.06 119 68.73 13.23 3.44 12.01 0.00 2.46 0.04 0.00 0.06 120 68.72 13.29 3.35 12.07 0.00 2.45 0.04 0.00 0.06 121 68.71 13.25 3.41 12.05 0.00 2.46 0.04 0.00 0.06 122 67.47 13.34 3.36 12.45 0.01 3.25 0.04 0.00 0.06 123 65.82 13.42 3.45 12.99 0.01 4.20 0.05 0.00 0.06 124 64.79 13.49 3.46 13.35 0.01 4.78 0.05 0.00 0.07 125 64.68 13.52 3.36 13.41 0.01 4.88 0.05 0.00 0.07 126 64.54 13.50 3.35 13.46 0.01 5.01 0.05 0.00 0.07 127 64.54 13.47 3.43 13.43 0.01 4.99 0.05 0.00 0.06 128 65.06 13.41 3.39 13.65 0.01 4.35 0.05 0.00 0.07 129 65.42 13.32 3.57 13.93 0.01 3.63 0.04 0.00 0.08 130 65.64 13.20 3.67 14.46 0.00 2.91 0.04 0.00 0.08 131 65.77 13.17 3.66 14.51 0.00 2.77 0.04 0.00 0.08 132 65.77 13.17 3.65 14.54 0.00 2.74 0.04 0.00 0.08 133 65.82 13.18 3.64 14.50 0.00 2.72 0.04 0.00 0.08 134 66.26 13.32 3.54 14.09 0.00 2.66 0.04 0.00 0.08 135 66.86 13.54 3.41 13.47 0.00 2.57 0.04 0.00 0.08 136 67.38 13.74 3.42 12.82 0.00 2.50 0.04 0.00 0.07 137 67.53 13.77 3.43 12.68 0.00 2.47 0.04 0.00 0.07 138 67.55 13.79 3.42 12.64 0.00 2.47 0.04 0.00 0.07 139 67.62 13.79 3.37 12.64 0.00 2.45 0.04 0.00 0.07 140 67.62 13.68 3.10 12.83 0.01 2.64 0.03 0.00 0.07 141 67.17 13.42 3.38 13.02 0.01 2.89 0.03 0.00 0.07 142 66.99 13.24 3.43 13.13 0.00 3.08 0.04 0.00 0.07 143 67.01 13.21 3.36 13.17 0.00 3.12 0.04 0.00 0.07 144 67.00 13.22 3.31 13.18 0.00 3.16 0.04 0.00 0.07 145 66.97 13.26 3.36 13.19 0.00 3.10 0.04 0.00 0.07 146 66.22 13.62 3.70 13.59 0.00 2.74 0.04 0.00 0.08 147 64.73 14.33 4.36 14.40 0.00 2.09 0.04 0.00 0.07 148 63.33 14.99 4.90 15.16 0.04 1.51 0.04 0.00 0.08 149 62.14 15.58 5.50 15.76 0.06 0.92 0.04 0.00 0.08 150 60.92 16.47 5.83 16.40 0.07 0.29 0.03 0.00 0.08 151 60.04 16.54 6.43 16.71 0.07 0.11 0.03 0.00 0.07 152 65.17 13.40 6.56 12.77 1.01 0.87 0.12 0.00 0.10 153 65.43 13.23 5.91 12.33 1.01 2.13 0.14 0.00 0.10 154 65.31 13.09 5.70 12.10 1.01 2.55 0.14 0.00 0.10 155 66.65 13.03 5.69 12.32 1.01 1.06 0.13 0.00 0.10 156 64.65 13.97 6.05 14.49 0.28 0.38 0.06 0.00 0.11 157 64.63 13.97 6.20 14.22 0.28 0.63 0.06 0.00 0.10 158 64.67 13.98 6.05 13.71 0.28 1.14 0.06 0.00 0.10 159 64.70 13.99 6.11 13.45 0.28 1.39 0.06 0.00 0.10 160 64.65 13.98 6.09 13.36 0.28 1.47 0.06 0.00 0.10 161 64.64 13.98 6.19 13.32 0.28 1.52 0.07 0.00 0.10 162 64.70 13.95 6.04 13.31 0.28 1.55 0.07 0.00 0.10 163 65.20 14.00 5.58 13.28 0.28 1.56 0.07 0.00 0.10 164 66.04 14.00 4.73 13.23 0.28 1.55 0.07 0.00 0.10 165 66.05 14.00 4.69 13.29 0.28 1.56 0.06 0.00 0.11 166 66.13 13.98 4.60 13.28 0.28 1.56 0.06 0.00 0.10 167 66.16 13.93 4.70 13.24 0.28 1.56 0.06 0.00 0.10 168 65.84 13.71 4.83 13.43 0.21 1.82 0.06 0.00 0.10 169 65.83 13.59 4.92 13.47 0.18 1.90 0.05 0.00 0.11 170 65.62 13.31 5.05 13.60 0.09 2.16 0.04 0.00 0.11 171 65.60 13.28 5.09 13.65 0.08 2.19 0.04 0.00 0.12 172 65.57 13.26 5.08 13.65 0.07 2.20 0.04 0.00 0.12 173 65.43 13.24 5.13 13.80 0.07 2.15 0.04 0.00 0.12 174 65.42 13.12 5.23 14.06 0.07 2.01 0.04 0.00 0.11 175 65.59 12.98 5.11 14.25 0.07 1.84 0.04 0.00 0.11 176 65.69 12.86 5.20 14.39 0.07 1.69 0.04 0.00 0.11 177 65.84 12.84 5.03 14.38 0.07 1.67 0.04 0.00 0.12 178 65.58 12.88 5.24 14.29 0.07 1.83 0.04 0.00 0.12 179 65.66 12.97 5.11 13.92 0.07 2.11 0.04 0.00 0.11 180 65.56 13.10 5.16 13.51 0.07 2.51 0.04 0.00 0.11 181 65.52 13.15 5.15 13.22 0.07 2.73 0.04 0.00 0.11 182 65.50 13.20 5.15 13.14 0.07 2.84 0.05 0.00 0.11 183 65.53 13.22 5.12 13.01 0.07 2.89 0.05 0.00 0.11 184 65.32 13.28 5.17 13.09 0.07 2.90 0.05 0.00 0.11 185 65.14 13.52 5.25 13.22 0.07 2.70 0.04 0.00 0.11 186 64.91 13.89 5.11 13.54 0.07 2.37 0.04 0.00 0.10 187 64.75 13.95 5.15 13.63 0.07 2.30 0.04 0.00 0.10 188 64.83 13.99 5.15 13.61 0.07 2.26 0.04 0.00 0.10 189 64.72 14.17 5.36 12.95 0.01 2.66 0.04 0.00 0.09 190 63.56 14.98 5.44 13.31 0.01 2.57 0.04 0.00 0.09 191 64.29 14.21 6.21 14.45 0.01 0.69 0.03 0.00 0.10 192 64.08 14.42 6.06 14.12 0.01 1.16 0.03 0.00 0.10 193 63.69 14.63 6.11 13.66 0.01 1.74 0.03 0.00 0.10 194 63.18 14.85 6.12 13.30 0.01 2.40 0.03 0.00 0.10 195 62.96 14.99 6.07 12.81 0.01 3.00 0.04 0.00 0.10 196 62.45 15.23 6.12 12.39 0.01 3.65 0.04 0.00 0.10 197 64.71 13.76 5.38 13.15 0.01 2.84 0.03 0.00 0.10 198 64.69 13.89 5.11 12.45 0.01 3.64 0.09 0.00 0.10 199 64.28 15.09 4.22 12.25 0.01 3.98 0.06 0.00 0.10 200 66.15 13.07 4.63 14.40 0.01 1.60 0.03 0.00 0.09 201 66.10 13.09 5.61 13.44 0.01 1.61 0.04 0.00 0.09 202 65.30 14.01 4.68 14.27 0.01 1.60 0.04 0.00 0.09 203 66.24 13.08 4.68 13.31 0.01 2.53 0.04 0.00 0.09 204 66.37 13.03 4.64 13.24 0.01 1.62 0.98 0.00 0.09 205 67.21 13.02 4.68 13.31 0.01 1.59 0.07 0.00 0.09 206 65.48 14.02 5.54 13.22 0.01 1.59 0.05 0.00 0.09 207 66.18 14.02 4.69 14.35 0.01 0.61 0.04 0.00 0.09 208 66.25 14.04 5.66 13.33 0.01 0.59 0.03 0.00 0.09 209 66.22 14.03 3.69 14.34 0.01 1.59 0.04 0.00 0.09 210 65.25 14.06 4.67 13.27 0.01 2.60 0.04 0.00 0.09 211 65.25 14.07 4.66 13.35 0.01 1.58 0.99 0.00 0.09 212 66.22 14.14 4.58 13.32 0.01 1.58 0.04 0.00 0.09 213 66.29 14.17 4.56 13.29 0.01 0.62 0.97 0.00 0.09 214 67.18 14.16 4.58 13.31 0.01 0.59 0.07 0.00 0.09 215 66.22 14.18 5.49 12.39 0.01 1.57 0.05 0.00 0.09 216 66.26 14.10 3.66 13.24 0.01 2.58 0.05 0.00 0.09 217 66.40 14.11 3.58 13.24 0.01 1.61 0.96 0.00 0.09 218 67.25 14.03 3.71 13.28 0.01 1.58 0.05 0.00 0.09 219 65.12 15.00 4.71 13.37 0.01 1.65 0.04 0.00 0.09 220 66.19 14.01 4.71 12.35 0.01 2.60 0.04 0.00 0.09 221 66.24 14.00 4.74 12.33 0.01 1.58 1.01 0.00 0.09 222 66.19 15.02 4.67 13.36 0.01 0.61 0.04 0.00 0.09 223 67.19 14.01 4.65 12.40 0.01 1.61 0.04 0.00 0.09 224 66.22 15.01 3.71 13.32 0.01 1.59 0.04 0.00 0.09 225 66.08 15.01 4.68 12.48 0.01 1.60 0.05 0.00 0.09 226 66.11 14.05 4.23 13.25 0.02 2.21 0.03 0.00 0.09 227 66.22 13.71 4.63 13.27 0.02 2.01 0.03 0.00 0.09 228 66.15 13.49 4.71 13.01 0.02 2.50 0.03 0.00 0.09 229 66.97 13.58 4.58 13.09 0.02 1.64 0.03 0.00 0.09 230 66.40 13.63 4.52 13.31 0.02 1.98 0.03 0.00 0.09 231 64.91 13.69 4.94 13.51 0.01 2.81 0.04 0.00 0.08 232 64.97 13.42 5.00 14.04 0.01 2.42 0.04 0.00 0.08 233 65.08 13.47 5.12 13.96 0.01 1.85 0.41 0.00 0.08 234 65.38 13.32 4.84 13.87 0.01 2.44 0.04 0.00 0.08 235 65.36 13.44 4.99 13.78 0.01 2.01 0.32 0.00 0.08

TABLE 2 Strain Anneal Soft Shear Young's SOC Temp. Temp. Temp. CTE Density Poisson Modulus Modulus Nm/ Example ° C. ° C. ° C. 10⁷/° C. g/cm³ Ratio (Mpsi) (Mpsi) MPa/cm Index 1 547.00 599.00 857.00 76.40 2.39 0.22 3.98 9.71 2 549.00 601.00 861.00 76.60 2.39 0.22 4.03 9.84 3 551.00 603.00 858.00 75.80 2.39 0.23 4.01 9.88 4 552.00 603.00 853.00 75.40 2.39 0.22 4.05 9.89 5 562.00 616.00 879.00 74.30 2.39 0.23 4.02 9.85 6 569.00 624.00 895.00 71.20 2.38 0.22 4.01 9.80 7 550.00 603.00 77.00 2.39 0.22 3.99 9.75 8 553.00 606.00 76.70 2.39 0.22 4.02 9.82 9 554.00 607.00 76.80 2.40 0.22 4.05 9.90 32.75 10 561.00 613.00 74.70 2.40 0.22 4.08 9.96 32.79 11 550.00 600.00 74.70 2.41 0.22 4.13 10.07 32.44 12 564.00 615.00 851.00 97.20 2.44 0.24 3.95 9.79 33.19 13 556.00 604.00 835.00 81.90 2.41 0.21 4.09 9.93 32.30 14 557.00 604.00 835.00 84.60 2.41 0.23 4.07 10.01 32.36 15 555.00 604.00 836.00 81.90 2.41 0.22 4.08 9.93 32.33 16 554.00 602.00 838.00 84.10 2.41 0.22 4.09 9.96 32.19 17 554.00 602.00 836.00 81.10 2.41 0.22 4.09 9.99 32.12 18 567.00 617.00 860.00 91.20 2.43 0.22 4.03 9.84 1.50 19 567.00 617.00 861.00 92.80 2.43 0.24 4.03 9.96 20 562.00 614.00 875.00 80.80 2.38 0.23 3.90 9.55 32.94 21 553.00 601.00 840.00 79.40 2.39 0.22 3.96 9.68 32.88 22 572.00 625.00 893.00 79.60 2.39 0.23 3.94 9.65 33.02 23 576.00 631.00 913.00 74.90 2.37 0.22 3.85 9.43 34.56 24 574.00 630.00 906.00 75.70 2.37 0.22 3.83 9.31 34.12 25 544.00 590.00 818.00 79.90 2.40 0.23 3.98 9.75 32.29 26 555.00 606.00 861.00 79.50 2.40 0.22 3.90 9.50 33.12 27 550.00 598.00 824.00 80.60 2.41 0.22 3.97 9.70 32.38 28 568.00 623.00 890.00 79.80 2.40 0.21 3.95 9.58 32.85 29 569.00 624.00 907.00 75.30 2.39 0.23 3.85 9.46 34.36 30 571.00 627.00 895.00 76.00 2.38 0.22 3.81 9.32 34.21 31 539.00 585.00 806.00 79.10 2.43 0.22 4.01 9.80 32.96 32 579.00 633.00 904.00 75.50 2.38 0.22 3.93 9.55 33 581.00 635.00 906.00 76.70 2.38 0.22 3.94 9.61 33.22 34 581.00 637.00 906.00 77.60 2.39 0.22 3.95 9.66 33.33 35 584.00 639.00 913.00 76.60 2.38 0.23 3.92 9.65 33.74 36 586.00 641.00 915.00 76.40 2.38 0.22 3.91 9.56 33.43 37 584.00 639.00 911.00 77.70 2.39 0.21 3.98 9.61 33.13 38 584.00 638.00 907.00 78.50 2.39 0.21 4.01 9.70 32.84 39 570.00 623.00 890.00 80.40 2.38 0.22 3.89 9.46 33.85 40 572.00 626.00 889.00 79.40 2.39 0.21 3.96 9.58 33.34 41 577.00 632.00 895.00 79.00 2.40 0.20 4.01 9.61 33.02 42 581.00 634.00 902.00 79.70 2.40 0.21 4.04 9.78 32.62 43 588.00 640.00 899.00 78.20 2.41 0.21 4.09 9.89 32.28 44 596.00 653.00 929.00 76.00 2.38 0.23 3.91 9.59 33.92 45 598.00 654.00 926.00 76.80 2.39 0.22 3.98 9.66 33.59 46 598.00 652.00 922.00 76.70 2.40 0.22 4.03 9.86 32.92 47 602.00 656.00 917.00 76.70 2.40 0.22 4.09 10.00 32.42 48 608.00 662.00 926.00 77.00 2.41 0.22 4.14 10.08 32.24 49 617.00 674.00 948.00 67.10 2.38 0.21 4.06 9.86 33.31 50 611.00 668.00 942.00 70.20 2.38 0.20 4.06 9.76 33.39 51 604.00 661.00 939.00 71.20 2.38 0.21 4.04 9.80 33.41 52 597.00 654.00 927.00 73.20 2.38 0.20 4.04 9.70 33.28 53 585.00 639.00 909.00 75.90 2.39 0.22 4.03 9.80 33.24 54 587.00 642.00 911.00 75.00 2.39 0.22 4.01 9.76 33.28 55 578.00 632.00 906.00 76.60 2.38 0.22 3.90 9.54 56 583.00 637.00 899.00 74.70 2.39 0.23 3.96 9.75 57 591.00 643.00 905.00 72.20 2.39 0.24 4.04 9.98 58 600.00 651.00 907.00 71.00 2.40 0.23 4.12 10.10 59 612.00 664.00 913.00 68.30 2.41 0.23 4.21 10.36 33.10 60 589.00 644.00 918.00 77.20 2.39 0.21 3.99 9.68 33.31 61 594.00 649.00 928.00 75.10 2.39 0.21 4.12 10.01 33.31 62 597.00 653.00 928.00 72.30 2.39 0.22 4.03 9.84 33.25 63 604.00 659.00 925.00 69.10 2.39 0.22 4.09 9.93 33.10 64 608.00 663.00 932.00 66.70 2.39 0.22 4.13 10.03 32.97 65 610.00 664.00 929.00 74.90 2.41 0.23 4.14 10.17 32.00 66 617.00 670.00 932.00 74.00 2.41 0.21 4.22 10.22 31.55 67 622.00 675.00 931.00 73.40 2.42 0.23 4.24 10.39 31.18 68 618.00 674.00 952.00 70.60 2.39 0.21 4.14 10.02 32.50 69 610.00 665.00 935.00 71.20 2.39 0.20 4.14 9.97 32.34 70 604.00 660.00 942.00 73.90 2.39 0.21 4.12 9.95 32.35 71 625.00 678.00 934.00 88.70 2.44 0.23 4.02 9.86 31.52 72 607.00 661.00 917.00 86.80 2.43 0.22 4.10 10.01 32.15 73 580.08 631.38 31.00 1.50 74 576.82 629.34 889.00 76.90 2.40 0.21 4.15 10.09 31.71 1.50 75 573.78 626.59 32.58 1.50 76 572.63 627.27 901.00 75.30 2.39 0.20 4.04 9.74 32.71 1.50 77 572.78 626.22 32.76 1.50 78 574.46 627.88 899.00 77.70 2.39 0.21 4.03 9.76 32.74 1.50 79 574.58 627.75 32.80 1.50 80 572.77 627.01 32.71 1.50 81 572.77 625.03 894.00 78.40 0.21 4.05 9.84 32.38 1.50 82 579.14 632.02 32.05 1.50 83 579.97 633.54 898.00 83.90 2.41 0.21 4.11 9.98 31.66 1.50 84 578.65 630.79 31.60 1.50 85 579.00 630.96 892.00 79.50 2.41 0.23 4.12 10.08 31.55 1.50 86 582.01 634.39 31.73 1.50 87 590.44 643.85 907.00 77.00 2.41 0.22 4.17 10.13 31.74 1.50 88 592.31 644.34 31.69 1.50 89 593.32 645.42 908.00 76.40 2.41 0.22 4.17 10.20 31.62 1.50 90 594.07 646.84 31.54 1.50 91 595.47 647.25 910.00 75.30 0.22 4.17 10.21 31.69 1.50 92 590.61 642.96 31.80 1.50 93 587.43 641.27 905.00 76.70 0.22 4.14 10.07 31.83 1.50 94 586.33 637.77 31.80 1.50 95 583.86 637.16 905.00 80.80 2.40 0.22 4.12 10.06 31.86 1.50 96 584.97 636.80 31.93 1.50 97 584.51 637.50 903.00 78.20 2.40 0.22 4.12 10.04 31.91 1.50 98 584.85 638.33 31.84 1.50 99 586.03 638.95 906.00 76.60 2.40 0.22 4.11 10.01 32.17 1.50 100 586.73 639.81 32.07 1.50 101 588.13 641.64 918.00 74.20 2.39 0.22 4.12 10.06 32.06 1.50 102 587.27 642.07 32.24 1.50 103 587.96 642.38 918.00 75.00 2.39 0.21 4.13 10.04 31.99 1.50 104 589.93 643.39 31.92 1.50 105 594.53 645.58 906.00 74.90 0.22 4.22 10.28 31.48 1.50 106 593.15 644.26 31.47 1.50 107 595.52 647.83 904.00 74.50 0.22 4.23 10.31 31.39 1.50 108 596.61 647.80 31.33 1.50 109 592.71 644.07 898.00 72.50 2.41 0.22 4.19 10.24 31.62 1.50 110 574.10 625.87 32.09 1.50 111 570.20 620.84 878.00 74.60 2.39 0.22 4.05 9.87 32.66 1.50 112 561.15 612.90 33.05 1.50 113 554.29 605.84 863.00 76.00 2.39 0.22 3.98 9.75 33.12 1.50 114 556.94 608.90 33.14 1.50 115 560.75 613.25 875.00 76.80 2.39 0.22 3.99 9.75 33.13 1.50 116 577.46 632.00 33.02 1.50 117 599.20 654.90 936.00 70.10 2.38 0.21 4.11 9.97 32.76 1.50 118 612.67 671.07 32.51 1.50 119 611.82 669.75 961.00 69.40 0.21 4.15 10.08 32.53 1.50 120 612.46 669.34 32.44 1.50 121 612.34 669.02 960.00 67.80 0.21 4.15 10.06 32.43 1.50 122 604.89 660.49 31.98 1.50 123 598.90 651.49 910.00 72.10 2.40 0.22 4.20 10.22 31.44 1.50 124 592.71 645.16 31.34 1.50 125 594.81 645.48 900.00 74.90 2.41 0.22 4.22 10.28 31.20 1.50 126 593.88 645.41 31.30 1.50 127 594.88 645.00 898.00 74.80 2.41 0.22 4.21 10.30 31.31 1.50 128 589.78 641.21 31.51 1.50 129 585.85 637.68 899.00 77.10 2.41 0.22 4.17 10.15 31.62 1.50 130 576.15 628.11 31.55 1.50 131 573.87 626.53 884.00 78.80 2.41 0.22 4.12 10.03 31.60 1.50 132 573.74 625.75 31.63 1.50 133 573.86 626.45 891.00 79.20 0.21 4.10 9.92 31.67 1.50 134 583.13 636.73 31.70 1.50 135 596.84 651.92 930.00 74.40 0.22 4.12 10.05 32.02 1.50 136 610.10 666.35 32.29 1.50 137 609.97 667.32 961.40 72.00 2.39 0.21 4.16 10.04 32.25 1.50 138 611.32 668.10 32.26 1.50 139 612.19 668.82 953.60 72.60 2.39 0.22 4.13 10.09 32.37 1.50 140 606.25 662.25 32.26 1.50 141 600.40 655.38 929.00 74.30 2.39 0.22 4.14 10.09 32.04 1.50 142 595.66 650.87 31.97 1.50 143 596.11 649.79 921.00 73.80 2.40 0.21 4.14 10.06 31.97 1.50 144 596.28 650.47 31.86 1.50 145 593.81 649.65 921.00 75.40 2.40 0.21 4.14 10.06 32.02 1.50 146 590.62 643.87 32.17 1.50 147 581.32 634.79 908.00 79.50 0.21 4.07 9.88 32.37 1.50 148 571.71 625.90 32.40 1.50 149 567.79 620.85 885.00 84.80 0.22 3.97 9.70 32.85 1.50 150 573.74 628.25 33.09 1.50 151 566.28 619.08 879.00 89.10 2.40 0.22 3.93 9.61 33.12 1.50 152 549.70 603.30 878.40 2.38 33.38 153 557.10 610.80 32.81 154 561.10 614.60 887.10 2.38 32.76 155 559.30 614.10 899.70 75.80 2.38 33.13 156 555.50 606.70 2.38 0.21 3.99 9.62 32.85 1.50 157 558.40 611.50 33.40 1.50 158 552.80 617.80 2.38 0.21 3.96 9.59 33.41 1.50 159 564.80 618.70 33.51 1.50 160 565.80 620.30 894.10 75.60 2.38 0.21 3.98 9.62 33.44 1.50 161 565.40 621.70 33.38 1.50 162 566.60 621.10 2.38 0.21 3.98 9.65 33.35 1.50 163 574.00 628.90 33.30 1.50 164 587.80 644.50 2.38 0.21 4.06 9.81 32.72 1.50 165 587.90 644.80 32.71 1.50 166 586.50 642.70 932.10 75.20 2.39 0.22 4.05 9.85 32.74 1.50 167 586.60 643.30 32.83 1.50 168 579.20 634.60 2.39 0.20 4.04 9.72 32.80 1.50 169 574.20 628.50 32.76 1.50 170 567.10 619.80 2.39 0.21 4.04 9.81 32.68 1.50 171 567.60 620.60 32.63 1.50 172 565.70 618.50 75.50 2.39 0.22 4.04 9.85 32.75 1.50 173 563.80 615.70 2.39 0.22 4.04 9.86 32.56 1.50 174 560.80 612.00 32.47 1.50 175 556.40 606.70 869.10 77.50 2.39 0.21 4.07 9.86 32.36 1.50 176 556.40 606.30 32.20 1.50 177 558.40 608.90 855.10 2.40 0.21 4.10 9.94 32.13 1.50 178 557.10 607.70 32.40 1.50 179 561.60 613.00 76.60 2.39 0.21 4.07 9.84 32.48 1.50 180 566.60 619.70 32.66 1.50 181 569.00 622.10 2.39 0.22 4.08 9.92 32.67 1.50 182 573.00 626.00 32.69 1.50 183 574.40 628.20 2.39 0.21 4.09 9.91 32.72 1.50 184 572.70 626.10 2.39 0.21 4.06 9.82 32.87 1.50 185 574.60 628.90 32.67 1.50 186 576.90 630.10 32.75 1.50 187 575.50 628.60 900.00 2.39 0.22 4.05 9.85 32.78 1.50 188 577.10 631.30 32.80 1.50 189 580.70 634.20 916.30 71.90 2.39 0.23 4.06 9.95 32.73 1.50 190 587.40 641.50 919.50 73.00 2.40 0.22 4.08 9.99 32.66 1.50 191 566.10 619.40 899.30 78.30 2.39 0.22 3.94 9.62 33.60 1.50 192 569.10 623.40 909.10 76.30 2.39 0.22 3.96 9.65 33.48 1.50 193 576.70 632.10 909.20 74.20 2.39 0.22 4.00 9.74 33.25 1.50 194 582.40 635.50 907.00 71.60 2.40 0.25 4.02 10.06 33.08 1.50 195 586.20 639.40 906.00 68.80 2.40 0.23 4.08 10.05 32.62 1.50 196 590.30 643.30 904.40 67.50 2.40 0.22 4.14 10.10 32.51 1.50 197 582.30 634.70 907.90 74.30 2.40 0.22 4.09 9.96 32.66 1.50 198 586.80 639.60 907.10 69.40 2.40 0.22 4.14 10.11 32.40 1.50 199 613.20 667.20 931.80 66.10 2.41 0.22 4.27 10.42 31.65 1.50 200 559.70 610.40 869.40 76.90 2.40 0.22 4.09 9.95 32.06 1.50 201 566.10 619.40 884.90 73.00 2.39 0.21 4.00 9.68 33.11 1.50 202 571.40 625.10 899.10 78.00 2.40 0.21 4.05 9.81 32.37 1.50 203 571.60 624.80 895.80 75.50 2.40 0.22 4.09 9.96 32.42 1.50 204 563.10 615.00 881.30 76.20 2.40 0.22 4.13 10.03 32.06 1.50 205 575.10 630.50 907.80 2.39 0.20 4.06 9.73 32.80 1.50 206 576.90 632.60 909.80 2.39 0.22 3.98 9.73 33.32 1.50 207 575.20 631.90 921.50 2.39 0.21 4.01 9.71 32.89 1.50 208 583.80 641.90 933.30 73.20 2.38 0.22 3.92 9.60 33.87 1.49 209 587.80 644.10 926.20 77.80 2.40 0.20 4.11 9.87 32.09 1.50 210 583.20 637.90 908.80 72.80 2.40 0.21 4.08 9.87 32.46 1.50 211 578.50 631.10 901.50 2.41 32.20 1.50 212 591.10 648.60 2.39 32.95 1.50 213 589.30 646.10 2.40 32.64 1.50 214 603.90 663.10 2.38 33.31 1.50 215 591.30 649.00 2.38 33.59 1.50 216 599.90 656.10 2.40 32.00 1.50 217 595.80 650.30 2.41 31.81 1.50 218 607.10 663.90 954.60 0.22 4.08 9.96 32.54 1.50 219 602.50 658.70 943.60 0.22 4.07 9.93 32.81 1.50 220 595.50 652.10 930.90 0.22 0.41 10.02 32.72 1.50 221 593.90 648.90 927.00 0.22 4.11 10.00 32.56 1.50 222 608.10 667.60 962.80 0.22 4.02 9.78 33.18 1.50 223 600.70 659.20 954.00 0.21 4.06 9.86 33.19 1.50 224 615.70 673.30 32.13 1.50 225 609.80 666.40 951.30 0.21 4.11 9.97 32.82 1.50 226 595.00 650.50 938.30 74.40 2.40 0.21 4.12 10.00 32.55 1.50 227 586.80 643.10 930.30 75.10 2.39 0.21 4.08 9.92 32.56 1.50 228 587.10 641.50 925.20 72.70 2.39 0.21 4.10 9.95 32.73 1.50 229 591.20 647.70 944.30 72.60 2.39 0.21 4.08 9.83 32.84 1.50 230 590.40 647.70 951.00 74.10 2.38 0.21 4.05 9.81 33.11 1.50 231 576.00 630.00 898.60 73.90 2.40 0.22 4.07 9.89 32.49 1.50 232 569.00 621.00 883.80 76.20 2.40 0.22 4.06 9.91 32.39 1.50 233 564.00 616.00 883.50 76.20 2.40 0.21 4.07 9.90 32.28 1.50 234 577.00 630.00 898.00 75.70 2.40 0.22 4.09 9.96 32.32 1.50 235 572.00 624.00 898.70 75.50 2.40 0.21 4.08 9.91 32.34 1.50

TABLE 3 CS DOL Indentation Example (MPa) (microns) Threshold (kgf) 1 49.4 37.5 2 48.0 37.5 3 49.3 37.5 4 46.9 37.5 5 49.0 37.5 6 47.6 37.5 7 53.0 37.5 8 52.5 37.5 9 730.4 49.6 37.5 10 710.6 51.0 37.5 11 735.7 44.0 37.5 12 977.8 49.2 12.5 13 760.8 47.0 22.5 14 761.6 46.9 32.5 15 771.8 44.9 27.5 16 778.6 42.7 27.5 17 792.0 42.6 32.5 18 12.5 19 12.5 20 773.9 49.7 42.5 21 734.0 45.3 35 22 799.5 53.6 40 23 728.9 51.1 35 24 757.3 52.7 42.5 25 711.6 38.0 35 26 758.3 50.1 32.5 27 721.0 45.3 30 28 782.0 54.7 32.5 29 725.5 53.1 32.5 30 752.3 53.3 27.5 31 699.0 39.2 17.5 32 59.0 17.5 33 767.1 61.1 32.5 34 766.0 61.3 37.5 35 764.0 60.8 40 36 764.7 62.0 32.5 37 778.9 62.0 40 38 784.0 62.4 27.5 39 718.8 56.7 32.5 40 734.0 54.0 37.5 41 762.2 52.6 42.5 42 776.8 51.6 35 43 794.9 50.4 35 44 773.2 54.7 32.5 45 795.8 52.5 37.5 46 829.9 47.9 47.5 47 854.5 48.4 42.5 48 868.2 46.7 40 49 754.8 46.1 37.5 50 762.4 48.3 42.5 51 762.7 50.7 42.5 52 772.0 51.6 35 53 764.5 51.3 40 54 766.8 51.6 40 55 52.6 47.5 56 52.9 42.5 57 42.1 32.5 58 38.0 32.5 59 34.2 27.5 60 789.7 56.8 50 61 788.9 54.5 42.5 62 779.9 49.9 32.5 63 763.9 44.6 32.5 64 740.5 40.0 35 65 877.8 47.2 22.5 66 894.7 44.9 22.5 67 911.3 43.6 17.5 68 808.2 47.6 22.5 69 815.3 49.4 22.5 70 811.2 50.4 22.5 71 1097.4 59.3 15 72 1030.8 56.6 >25 73 851.5 44.5 12.5 74 846.2 43.2 17.5 75 826.1 44.3 27.5 76 823.1 44.8 32.5 77 827.4 44.5 30 78 846.9 44.6 27.5 79 837.1 43.2 42.5 80 833.1 44.0 37.5 81 839.9 43.2 22.5 82 870.4 45.8 17.5 83 895.2 46.4 17.5 84 894.0 46.7 17.5 85 892.9 46.7 12.5 86 887.9 45.2 12.5 87 886.9 42.9 12.5 88 884.3 42.5 22.5 89 886.8 40.8 22.5 90 868.0 41.8 22.5 91 877.3 40.8 12.5 92 864.6 42.3 22.5 93 871.9 43.4 22.5 94 875.0 44.6 17.5 95 868.3 45.1 12.5 96 867.5 44.9 17.5 97 867.0 44.8 12.5 98 860.8 45.2 22.5 99 837.8 45.5 17.5 100 823.4 46.4 20 101 820.1 46.7 22.5 102 812.5 47.3 22.5 103 844.0 45.0 17.5 104 835.2 41.7 17.5 105 846.6 42.9 22.5 106 846.9 38.4 17.5 107 850.3 37.8 17.5 108 857.6 38.2 12.5 109 845.8 38.5 17.5 110 817.2 37.6 22.5 111 793.0 39.3 30 112 778.9 39.6 27.5 113 767.8 38.0 27.5 114 770.6 39.3 17.5 115 766.0 39.9 27.5 116 795.9 42.0 27.5 117 798.8 45.1 27.5 118 791.5 46.5 32.5 119 794.2 46.1 32.5 120 798.7 46.3 27.5 121 801.4 46.2 32.5 122 838.2 43.1 25 123 870.8 40.0 22.5 124 886.9 37.2 12.5 125 896.6 37.7 12.5 126 892.6 36.9 12.5 127 891.2 37.2 17.5 128 888.5 39.3 12.5 129 880.8 42.1 17.5 130 855.8 44.7 12.5 131 849.4 45.2 12.5 132 860.3 44.7 12.5 133 851.2 45.1 17.5 134 864.4 47.0 12.5 135 873.9 48.0 17.5 136 840.3 48.3 22.5 137 842.2 47.3 32.5 138 839.3 47.0 37.5 139 836.8 47.3 32.5 140 843.5 46.8 27.5 141 853.2 47.1 27.5 142 855.9 46.1 27.5 143 865.4 44.9 22.5 144 868.6 45.1 27.5 145 866.0 45.9 27.5 146 873.0 46.3 32.5 147 891.7 46.8 27.5 148 894.5 48.5 37.5 149 869.8 51.7 37.5 150 903.8 55.3 42.5 151 853.8 54.5 37.5 152 712.8 51.3 37.5 153 739.3 48.9 32.5 154 711.8 47.7 32.5 155 741.1 52.7 37.5 156 32.5 157 22.5 158 22.5 159 32.5 160 32.5 161 27.5 162 32.5 163 37.5 164 42.5 165 37.5 166 37.5 167 42.5 168 32.5 169 37.5 170 32.5 171 27.5 172 37.5 173 27.5 174 32.5 175 22.5 176 12.5 177 22.5 178 17.5 179 27.5 180 22.5 181 45 182 42.5 183 47.5 184 42.5 185 37.5 186 42.5 187 37.5 188 37.5

Table 4 compares physical properties of the glasses described herein, labeled Glass 2 and having the composition 64.65 mol % SiO₂, 13.93 mol % Al₂O₃, 5.11 mol % B₂O₃, 13.75 mol % Na₂O, 0 mol % K₂O, 2.38 mol % MgO, 0.14 mol % CaO, and 0.08 mol % SnO₂, with those properties of Glass 1, which has the composition having the composition 68.84 mol % SiO₂, 10.63 mol % Al₂O₃, 0 mol % B₂O₃, 14.86 mol % Na₂O, 0.02 mol % K₂O, 5.43 mol % MgO, 0.04 mol % CaO, and 0.17 mol % SnO₂, and is described in U.S. patent application Ser. No. 13/533,298, by Matthew J. Dejneka et al., entitled “Ion Exchangeable Glass With High Compressive Stress,” which claims priority from U.S. Provisional Patent Application No. 61/503,734, filed on Jul. 1, 2011 and having the same title; and Glass 2, which has the composition 67.45 mol % SiO₂, 12.69 mol % Al₂O₃, 3.67 mol % B₂O₃, 13.67 mol % Na₂O, 0.02 mol % K₂O, 2.36 mol % MgO, 0.03 mol % CaO, and 0.09 mol % SnO₂, and is described in U.S. Provisional Patent Application No. 61/653,489, filed on May 31, 2012, by Matthew J. Dejneka et al., entitled “Zircon Compatible, Ion Exchangeable Glass With High Damage Resistance,” and U.S. Provisional Patent Application No. 61/748,981, filed on Jan. 4, 2013, by Matthew J. Dejneka et al., and having the same title.

TABLE 4 Glass 1 2 3 Anneal Point (° C.) 650 629 644 Strain Point (° C.) 601 576 589 Softening Point (° C.) 891.7 900 922.4 Density (g/cm³) 2.432 2.39 2.403 Poisson's Ratio 0.205 0.216 0.213 Shear Modulus (Mpsi) 4.287 4.051 4.142 Young's Modulus (Mpsi) 10.336 9.851 10.046 Liquidus Temperature (° C.) 1020 1000 1005 Liquidus Viscosity (kPoise) 1000 1850 2210 Primary Devit Phase Forsterite Nepheline Forsterite Zircon Breakdown 1200 1183 1230 Temperature (° C.) Zircon Breakdown 30.4 71.4 33.4 Viscosity (kPoise) 200 Poise Temperature (° C.) 1665 1679 1757 35k Poise Temperature (° C.): 1190 1226 1227 Refractive Index 1.50030 1.49844 1.49836 SOC (nm/MPa/cm) 29.64 32.78 31.94

The glasses described herein are resistant to both chipping and scratching, making it well suited for use in cover plates, touch screens, watch crystals, solar concentrators, windows, screens, containers, and other applications that require strong and tough glass with good scratch resistance.

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims. 

The invention claimed is:
 1. A glass comprising: a. at least about 50 mol % SiO₂; b. at least about 10 mol % R₂O, wherein R₂O comprises at least about 10 mol % Na₂O; c. from 12 mol % to about 22 mol % Al₂O₃, wherein −1.61 mol %≦Al₂O₃(mol %)−R₂O(mol %)≧2 mol %; d. from greater than 0 mol % up to 5 mol % B₂O₃, wherein B₂O₃(mol %)−(R₂O(mol %)−Al₂O₃(mol %))≧4.5 mol %; and e. at least 0.1 mol % of at least one of MgO and ZnO, wherein the glass is ion exchangeable.
 2. The glass of claim 1, wherein the glass comprises: at least about 50 mol % SiO₂, from 12 mol % to about 22 mol % Al₂O₃; from about 4.5 mol % to 5 mol % B₂O₃; from about 10 mol % to about 20 mol % Na₂O; from 0 mol % to about 5 mol % K₂O; at least about 0.1 mol % of at least one of MgO, ZnO, or combinations thereof, wherein 0 mol %≦MgO≦6 and 0≦ZnO≦6 mol %; and, optionally, at least one of CaO, BaO, and SrO, wherein 0 mol %≦CaO+SrO+BaO≦2 mol %.
 3. The glass of claim 2, wherein the glass comprises from about 60 to 66 mol % SiO₂.
 4. The glass of claim 1, wherein the glass comprises greater than 4.5 mol % B₂O₃ in which boron cations are three-fold coordinated.
 5. The glass of claim 1, wherein the glass is ion exchanged and has a layer under a compressive stress of at least about 600 MPa, the layer extending from a surface of the glass into the glass to a depth of layer of at least about 30 μm.
 6. The glass of claim 5, wherein the compressive stress is at least about 800 MPa.
 7. The glass of claim 5, wherein the glass has a Vickers crack initiation threshold of at least about 30 kgf.
 8. A glass comprising: at least about 50 mol % SiO₂; at least about 10 mol % R₂O, wherein R₂O comprises at least about 10 mol % Na₂O; from 12 mol % to about 22 mol % Al₂O₃; greater than about 2.5 mol % to 5 mol % B₂O₃; and at least 0.1 mol % of at least one of MgO and ZnO, wherein B₂O₃(mol %)−(R₂O(mol %)−Al₂O₃(mol %))≧4.5 mol %, wherein the glass has a zircon breakdown temperature at which the viscosity of the glass is greater than about 40 kPoise.
 9. The glass of claim 8, wherein the glass comprises: at least about 50 mol % SiO₂, from 12 mol % to about 22 mol % Al₂O₃; from about 4.5 mol % to 5 mol % B₂O₃; from about 10 mol % to about 20 mol % Na₂O; from 0 mol % to about 5 mol % K₂O; at least about 0.1 mol % of at least one of MgO and ZnO, wherein 0 mol %≦MgO≦6 and 0≦ZnO≦6 mol %; and, optionally, at least one of CaO, BaO, and SrO, wherein 0 mol %≦CaO+SrO+BaO≦2 mol %.
 10. The glass of claim 9, wherein the glass comprises from about 60 to about 66 mol % SiO₂.
 11. The glass of claim 8, wherein the glass comprises greater than about 4.5 mol % B₂O₃ in which boron cations are three-fold coordinated.
 12. The glass of claim 9, wherein the glass is ion exchanged and has a layer under a compressive stress of at least about 600 MPa, the layer extending from a surface of the glass into the glass to a depth of layer of at least about 30 μm.
 13. The glass of claim 12, wherein the compressive stress is at least about 800 MPa.
 14. The glass of claim 12, wherein the glass has a Vickers crack initiation threshold of at least about 30 kgf.
 15. A glass, wherein the glass is ion exchanged and has a Vickers crack initiation threshold of at least about 30 kgf, the glass comprising: a. at least about 60 mol % SiO₂; b. at least about 10 mol % R₂O, wherein R₂O comprises at least about 10 mol % Na₂O; c. from 12 mol % to about 22 mol % Al₂O₃, wherein −1.61 mol %≦Al₂O₃(mol %)−R₂O(mol %)≦2 mol %; d. from greater than 0 mol % up to 5 mol % B₂O₃, wherein B₂O₃(mol %)−(R₂O(mol %)−Al₂O₃(mol %))≧4.5 mol %; and e. at least 0.1 mol % of at least one of MgO and ZnO, wherein the glass is ion exchangeable.
 16. The glass of claim 15, wherein the glass comprises: at least about 50 mol % SiO₂, from 12 mol % to about 22 mol % Al₂O₃; from about 4.5 mol % to 5 mol % B₂O₃; from about 10 mol % to about 20 mol % Na₂O; from 0 mol % to about 5 mol % K₂O; at least about 0.1 mol % of at least one of MgO and ZnO, wherein 0 mol %≦MgO≦6 and 0≦ZnO≦6 mol %; and, optionally, at least one of CaO, BaO, and SrO, wherein 0 mol %≦CaO+SrO+BaO≦2 mol %.
 17. The glass of claim 16, wherein the glass comprises from about 60 to about 66 mol % SiO₂.
 18. The glass of claim 15, wherein the glass comprises greater than about 4.5 mol % B₂O₃ in which boron cations are three-fold coordinated.
 19. The glass of claim 15, wherein the glass has a layer under a compressive stress of at least about 600 MPa, the layer extending from a surface of the glass into the glass to a depth of layer of at least about 30 μm.
 20. The glass of claim 19, wherein the compressive stress is at least about 800 MPa.
 21. The glass of claim 15, wherein the Vickers crack initiation threshold is in a range from about 30 kgf to about 35 kgf. 